CN116826024A - Doped porous hard carbon composite material and preparation method and application thereof - Google Patents

Doped porous hard carbon composite material and preparation method and application thereof Download PDF

Info

Publication number
CN116826024A
CN116826024A CN202311031240.3A CN202311031240A CN116826024A CN 116826024 A CN116826024 A CN 116826024A CN 202311031240 A CN202311031240 A CN 202311031240A CN 116826024 A CN116826024 A CN 116826024A
Authority
CN
China
Prior art keywords
hard carbon
nitrogen
seconds
sodium
carbon composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311031240.3A
Other languages
Chinese (zh)
Inventor
宋敬川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Nabonn New Materials Co ltd
Original Assignee
Shenzhen Nabonn New Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Nabonn New Materials Co ltd filed Critical Shenzhen Nabonn New Materials Co ltd
Priority to CN202311031240.3A priority Critical patent/CN116826024A/en
Publication of CN116826024A publication Critical patent/CN116826024A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The embodiment of the invention discloses a preparation method of a doped porous hard carbon composite material, which comprises the following steps: mixing a biomass raw material with a heteroatom compound containing nitrogen and/or phosphorus, ball milling, introducing ammonia-containing gas, and heating to react to obtain a precursor material; and depositing sodium vanadate on the surface of the precursor material by an atomic vapor deposition method to obtain the sodium vanadate coated hard carbon composite material. According to the composite material, the heteroatom compound containing nitrogen and/or phosphorus is added in the hard carbon preparation process, ammonia gas is introduced, active points of the material are improved by reaction at high temperature, the sodium storage performance of the material is improved, a hole structure is formed in the carbonization process by doping the heteroatom with the hard carbon, the sodium storage performance of the material is further improved, sodium vanadate is deposited by an atomic vapor deposition method, and the cycle performance is improved; meanwhile, sodium precipitation of the material is not easy to occur, and the safety performance is improved.

Description

Doped porous hard carbon composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a secondary battery material, in particular to a doped porous hard carbon composite material, and a preparation method and application thereof.
Background
Along with the improvement of the safety performance requirements of the sodium ion battery in the market, the negative electrode material is a main factor influencing the safety of the sodium ion battery in the charging process, and the safety performance is influenced by sodium precipitation caused by deposition of sodium ions on the surface of hard carbon in the high-rate charging process because the sodium ion battery has larger sodium ion particle size and poorer electron conductivity of hard carbon. One of the methods for reducing the risk of sodium precipitation is to improve the dynamic performance of the hard carbon negative electrode material to avoid sodium precipitation of the material, and cladding doping is the simplest and most effective method for improving the electronic and ionic conductivity of the hard carbon material, for example, doping a metal element with high electronic conductivity and solid electrolyte thereof to improve the electronic conductivity of the material, or cladding a compound containing sodium ion conductivity on the surface of the material to improve the exchange rate of sodium ions in the charge and discharge process and improve the rate capability. In the prior art, the hard carbon anode material is coated with polypyrrole and other materials, and the hard carbon ball is used as a matrix, and the polypyrrole layer is coated on the matrix to improve the electronic conductivity of the anode material, but the ionic conductivity of the material is not improved, so that the improvement of the multiplying power performance and the safety performance of the anode material is not obvious.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the doped porous hard carbon composite material for improving the safety performance of the hard carbon material in the high-rate charging process, which improves the sodium storage performance of the material, increases active points, improves the electronic conductivity of hard carbon, reduces the risk of sodium precipitation by coating sodium vanadate to improve a discharge voltage platform, and improves the safety of the composite material serving as a sodium ion anode material in the charging process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the technical object of the first aspect of the present invention is to provide a method for preparing a doped porous hard carbon composite material, comprising:
mixing a biomass raw material with a heteroatom compound containing nitrogen and/or phosphorus, ball milling, introducing ammonia-containing gas, and heating to react to obtain a precursor material;
and depositing sodium vanadate on the surface of the precursor material by an atomic vapor deposition method to obtain the sodium vanadate coated hard carbon composite material.
Further, the nitrogen and/or phosphorus containing heteroatom compound is selected from at least one of melamine, phosphoric acid, urea and pyrrole.
Further, the biomass raw material and the heteroatom compound containing nitrogen and/or phosphorus are mixed according to the weight ratio of 100: 1-5.
Further, the biomass raw material is lignocellulose such as straw, tree, fruit shell and the like in the agriculture and forestry production process, and the biomass raw material is preferably at least one of coconut shells, apricot shells, straw, cotton stalks and walnut shells.
Further, the ammonia-containing gas is a mixed gas of ammonia and an inert gas, preferably a mixed gas of ammonia and nitrogen. Ammonia in the mixed gas: the volume ratio of the inert gas is 1-5:10, the flow rate of the mixed gas is 100-500mL/min.
Further, ammonia-containing gas is introduced, and the temperature is raised to 300-500 ℃ for carbonization reaction for 1-6h.
Further, the atomic vapor deposition (ALD) process sequentially includes: introducing sodium vanadate, purging with nitrogen, introducing an oxygen source, purging with nitrogen, introducing water, purging with nitrogen, and repeating the above process for 10-100 times.
As one of more specific embodiments, for example, (1) sodium vanadate is fed for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; (1) - (6) cycle 10-100 cycles.
The technical object of the second aspect of the present invention is to provide a doped porous hard carbon composite material prepared by the above method.
The technical purpose of the third aspect of the invention is to provide the application of the doped porous hard carbon composite material as a negative electrode material of a sodium ion battery.
The implementation of the technical scheme of the invention has the following beneficial effects:
(1) According to the composite material, the heteroatom compound containing nitrogen and/or phosphorus is added in the hard carbon preparation process, ammonia gas is introduced, nitrogen and/or phosphorus doping is formed through reaction at high temperature, active points of the material are improved, the dynamic performance of the material is improved, a hole structure is formed in the carbonization process through doping the heteroatom compound, the specific surface area is increased, and the sodium storage performance of the material is improved.
(2) The material of the invention finally adopts an atomic vapor deposition method to deposit sodium vanadate, and has the advantages of high deposition density, stable structure, high consistency, controllable deposition thickness process and the like, and improves the cycle performance; meanwhile, the sodium-embedded battery of the sodium vanadate material is high, so that sodium precipitation of the material is not easy to occur in the battery charging process, and the safety performance is improved.
(3) The sodium vanadate deposited by adopting the atomic vapor deposition method has the characteristic of high sodium ion intercalation and deintercalation rate in the charge and discharge process, reduces the loss of sodium ions in the charge and discharge process, improves the primary efficiency and improves the multiplying power performance.
Drawings
Fig. 1 is an SEM image of the doped hard carbon composite material prepared in example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Step S1: adding 100g of coconut shell and 3g of melamine into a high-pressure ball mill, uniformly mixing, and carbonizing for 3 hours at 400 ℃ under the mixed atmosphere of ammonia gas/nitrogen (volume ratio, ammonia gas: nitrogen=3:10) at the flow rate of 300mL/min to obtain a precursor material;
step S2: transferring the precursor material into the cavity by an atomic vapor deposition method according to the following procedure, (1) sodium vanadate for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; and (3) circulating for 50 circles from the steps (1) - (6), and depositing sodium vanadate on the surface of the precursor material to obtain the sodium vanadate coated hard carbon composite material.
Example 2
Step S1: adding 100g of apricot shells and 1g of phosphoric acid into a high-pressure ball mill, uniformly mixing, and carbonizing for 6 hours at the temperature of 300 ℃ under the mixed atmosphere of ammonia gas/nitrogen gas (volume ratio, ammonia gas: nitrogen=1:10) at the flow rate of 100mL/min to obtain a precursor material;
step S2: transferring the precursor material into the cavity by an atomic vapor deposition method according to the following procedure, (1) sodium vanadate for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; and (3) circulating for 10 circles from the steps (1) - (6), and depositing sodium vanadate on the surface of the precursor material to obtain the sodium vanadate coated hard carbon composite material.
Example 3
Step S1: adding 100g of walnut shell and 5g of urea into a high-pressure ball mill, uniformly mixing, and carbonizing for 1h at the temperature of 500 ℃ under the mixed atmosphere of ammonia gas/nitrogen gas (volume ratio, ammonia gas: nitrogen gas=5:10) at the flow rate of 500mL/min to obtain a precursor material;
step S2: transferring the precursor material into the cavity by an atomic vapor deposition method according to the following procedure, (1) sodium vanadate for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; and (3) circulating for 100 circles from the steps (1) - (6), and depositing sodium vanadate on the surface of the precursor material to obtain the sodium vanadate coated hard carbon composite material.
Comparative example 1
Unlike example 1, melamine was not added, and otherwise the same as in example 1, specifically:
step S1: adding 100g of coconut shells into a high-pressure ball mill, uniformly mixing, and carbonizing for 3 hours at the temperature of 400 ℃ under the mixed atmosphere of ammonia gas/nitrogen gas (volume ratio, ammonia gas: nitrogen=3:10) at the flow rate of 300mL/min to obtain a precursor material;
step S2, transferring the precursor material into a cavity by an atomic vapor deposition method, wherein the precursor material is prepared according to the following process, (1) sodium vanadate for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; and (3) circulating for 50 circles from the steps (1) - (6), and depositing sodium vanadate on the surface of the precursor material to obtain the sodium vanadate coated hard carbon composite material.
Comparative example 2
Unlike example 1, the ammonia/nitrogen mixture was not introduced, and the other steps were the same as in example 1, specifically:
step S1: adding 100g of coconut shell and 3g of melamine into a high-pressure ball mill, uniformly mixing, heating to 400 ℃ and carbonizing for 3 hours to obtain a precursor material;
step S2: transferring the precursor material into the cavity by an atomic vapor deposition method according to the following procedure, (1) sodium vanadate for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; and (3) circulating for 50 circles from the steps (1) - (6), and depositing sodium vanadate on the surface of the precursor material to obtain the sodium vanadate coated hard carbon composite material.
Comparative example 3
Unlike example 1, sodium vanadate was coated in other ways, specifically:
step S1: adding 100g of coconut shell and 3g of melamine into a high-pressure ball mill, uniformly mixing, and carbonizing for 3 hours at 400 ℃ under the mixed atmosphere of ammonia gas/nitrogen (volume ratio, ammonia gas: nitrogen=3:10) at the flow rate of 300mL/min to obtain a precursor material;
step S2: adding 10g of sodium vanadate into 500g of ethanol for uniform dispersion, adding 100g of precursor material for uniform dispersion, spray drying, and carbonizing at 800 ℃ for 3 hours to obtain the sodium vanadate coated hard carbon composite material.
Comparative example 4
Unlike example 1, sodium iron phosphate was used instead of sodium vanadate, except that the procedure was as in example 1, except that:
step S1: adding 100g of coconut shell and 3g of melamine into a high-pressure ball mill, uniformly mixing, and carbonizing for 3 hours at 400 ℃ under the mixed atmosphere of ammonia gas/nitrogen (volume ratio, ammonia gas: nitrogen=3:10) at the flow rate of 300mL/min to obtain a precursor material;
step S2: transferring the precursor material into the cavity by an atomic vapor deposition method according to the following procedure, (1) sodium iron phosphate for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; and (3) circulating for 50 circles from the steps (1) - (6), depositing sodium vanadate on the surface of the precursor material to obtain the sodium iron phosphate coated hard carbon composite material, and obtaining the sodium iron phosphate coated hard carbon composite material.
Performance testing of the materials prepared in the above examples and comparative examples:
(1) SEM test
The hard carbon composite material prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 1. As can be seen from FIG. 1, the hard carbon composite material prepared in example 1 is in the form of particles having a particle diameter D50 of between (5 and 10) μm.
(2) Physical and chemical Property measurement
The hard carbon composites prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to measurement of interlayer spacing (D002), specific surface area, tap density, particle size D50, and powder conductivity. The testing method is tested according to the method of the national standard GBT-24533-2019 lithium ion battery graphite anode material; meanwhile, the powder conductivity (pressure 50 Mpa) of the material was measured by a four-probe tester. The test results are shown in Table 1.
Table 1.
(3) Button cell testing
The hard carbon composite materials in examples 1-3 and comparative examples 1-4 are used as negative electrode materials of sodium ion batteries to be assembled into button batteries, and the specific preparation method of the negative electrode materials is as follows: according to the hard carbon composite material: CMC: SBR: SP: h 2 Mixing the materials according to the mass ratio of O of 94:2.5:1.5:2:150 to prepare a negative plate; sodium flakes as counter electrode; the electrolyte adopts NaPF 6 (the solvent is EC: DEC: PC: propylene glycol Polymer)Oxypropylene ether = 1:2:1:0.05, concentration 1.3 mol/L) as electrolyte; the diaphragm adopts a composite film of polyethylene PE, polypropylene PP and polyethylene propylene PEP. The button cell assembly was performed in an argon filled glove box. Electrochemical performance is carried out on a Wuhan blue electric CT2001A type battery tester, the charging and discharging voltage range is 0.00V to 2.0V, the charging and discharging rate is 0.1C, the first discharge capacity and the first efficiency of the button battery are tested, and the testing method is measured according to the GBT-24533-2019 standard of graphite negative electrode materials of lithium ion batteries. The test results are shown in Table 2.
Table 2.
As can be seen from tables 1 and 2, the hard carbon composite material of the example is superior to the comparative example in specific capacity and primary efficiency because the present invention utilizes the pore-forming effect of nitrogen/phosphorus and more active sites provided thereby to increase specific capacity, reduce irreversible capacity thereof and increase primary efficiency.
(4) Soft package battery test:
the hard carbon composites of examples 1 to 3 and comparative examples 1 to 4 were slurried and coated to prepare a negative electrode sheet using a layered oxide as a positive electrode and NaPF 6 (the solvent is EC: DEC: PC: propylene glycol polyoxypropylene ether=1:2:1:0.05, and the concentration is 1.3 mol/L) as an electrolyte to prepare a 5Ah soft package battery.
The liquid absorbing capacity of the negative electrode sheet was tested.
Testing the cycle performance: the charge and discharge current is 2.0C/2.0C, the voltage range is 1-4.0V, and the cycle number is 500.
Testing rate performance: and testing the constant current ratio of the soft package battery under the charging conditions of initial cycle charging DCR and 2C.
The test results are shown in Table 3.
Table 3.
As can be seen from Table 3, the liquid absorption speed and the constant current ratio of the negative electrode sheets in examples 1-3 are obviously better than those of the comparative examples, and the analysis reasons are that: the material has high specific surface area to promote the liquid absorption speed of the material, and meanwhile, the material promotes the powder conductivity and the electron conductivity of the material due to the nitrogen and phosphorus doping of the inner core, and the sodium vanadate is coated on the outer core to promote the sodium ion transmission rate, so that the rate performance (constant current ratio) is improved, and the sodium vanadate has the characteristic of stable structure, reduces the side reaction and improves the cycle performance.
(5) Safety performance test
1) Needling experiment
The pouch cells were prepared as in (4) using the materials of examples 1 to 3 and comparative examples 1 to 4, 10 cells were taken each, and after the cells were fully charged, a nail having a diameter of 5mm was passed through the center of the cell, and a temperature tester was installed at the battery post, and the nail was left in the cell, and the cell conditions were observed, and the cell temperature was measured and the pass rate (no fire/total cell) was observed. See table 4 below.
2) Overcharge test
And similarly, 10 soft-packed batteries are respectively taken, the charging is stopped after the batteries are charged to 1.5 times of the regulated upper limit voltage of the batteries by constant current with the 1C multiplying power, the charging is observed for 1h, and whether the batteries are ignited or not is observed. The results are shown in Table 4.
Table 4.
As can be seen from table 4, the local temperature of the battery is too high when the battery is abnormally used such as needling short circuit, and sodium vanadate is deposited on the surface of the battery by the material in the embodiment, so that the battery has the characteristics of stable structure and low impedance, the heat diffusion rate is high, the surface temperature of the battery is reduced, and the needling performance is improved; and the sodium vanadate coated on the outer layer has the characteristic of high voltage platform, so that lithium is not easy to separate out in the overcharging process of the battery, and fire explosion is not easy to generate.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. A method of preparing a doped porous hard carbon composite comprising:
mixing a biomass raw material with a heteroatom compound containing nitrogen and/or phosphorus, ball milling, introducing ammonia-containing gas, and heating to react to obtain a precursor material;
and depositing sodium vanadate on the surface of the precursor material by an atomic vapor deposition method to obtain the sodium vanadate coated hard carbon composite material.
2. The method according to claim 1, wherein the nitrogen and/or phosphorus-containing heteroatom compound is at least one selected from the group consisting of melamine, phosphoric acid, urea and pyrrole.
3. The method of claim 1, wherein the biomass feedstock and nitrogen and/or phosphorus containing heteroatom compounds are present in a weight ratio of 100: 1-5.
4. The method of claim 1, wherein the biomass feedstock is selected from at least one of coconut shells, apricot shells, straw, cotton stalks, and walnut shells.
5. The method according to claim 1, wherein the ammonia-containing gas is a mixed gas of ammonia gas and inert gas, ammonia gas: the volume ratio of the inert gas is 1-5:10, the flow rate of the mixed gas is 100-500mL/min.
6. The preparation method according to claim 1, wherein ammonia-containing gas is introduced, and the temperature is raised to 300-500 ℃ for carbonization reaction for 1-6 hours.
7. The method according to claim 1, wherein the atomic vapor deposition process sequentially comprises: introducing sodium vanadate, purging with nitrogen, introducing an oxygen source, purging with nitrogen, introducing water, purging with nitrogen, and repeating the above process for 10-100 times.
8. The method according to claim 7, wherein the atomic vapor deposition method comprises the steps of: (1) sodium vanadate is introduced for 1 second; (2) nitrogen purge for 60 seconds; (3) introducing an oxygen source for 5 seconds; (4) nitrogen purge for 5 seconds; (5) introducing water for 0.05 seconds; (6) nitrogen purge for 50 seconds; (1) - (6) cycle 10-100 cycles.
9. A doped porous hard carbon composite prepared by the method of any one of claims 1-8.
10. Use of the doped porous hard carbon composite of claim 9 as a negative electrode material for sodium ion batteries.
CN202311031240.3A 2023-08-16 2023-08-16 Doped porous hard carbon composite material and preparation method and application thereof Pending CN116826024A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311031240.3A CN116826024A (en) 2023-08-16 2023-08-16 Doped porous hard carbon composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311031240.3A CN116826024A (en) 2023-08-16 2023-08-16 Doped porous hard carbon composite material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116826024A true CN116826024A (en) 2023-09-29

Family

ID=88116916

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311031240.3A Pending CN116826024A (en) 2023-08-16 2023-08-16 Doped porous hard carbon composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116826024A (en)

Similar Documents

Publication Publication Date Title
CN106099041B (en) Lithium titanate composite negative electrode piece and lithium titanate battery
CN114420939B (en) High-rate spherical hard carbon composite material and preparation method and application thereof
CN112216814B (en) Electrode plate, secondary battery, preparation method of secondary battery and device containing secondary battery
CN109037659A (en) A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material
CN113764644B (en) Quick-filling composite graphite material and preparation method thereof
CN114613974B (en) Long-life quick-charging type lithium ion battery cathode material and preparation method thereof
JP7106762B2 (en) Positive electrode sheet, manufacturing method thereof, and lithium ion secondary battery
CN102034971A (en) Lithium-ion battery lithium iron phosphate/polypyrrole pyridine composite anode material and preparation method thereof
CN115566170B (en) Preparation method of high-energy-density quick-charging lithium ion battery anode material
EP4164000A1 (en) Hard carbon composite material, preparation method therefor, and use thereof
CN114447305A (en) Multi-element carbon-based rapid-charging negative electrode composite material and preparation method thereof
CN113889593A (en) Preparation method of hard carbon-coated soft carbon composite material
CN112310352A (en) Negative electrode active material and secondary battery
CN114497506A (en) Hard carbon-inorganic lithium salt composite electrode material and preparation method and application thereof
CN114678505B (en) Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof
CN114583093A (en) Preparation method and application of high-energy-density hard carbon composite negative electrode material
CN105845886A (en) Negative electrode material for ion battery and preparation method of negative electrode material
CN114094070A (en) Titanium niobate-coated hard carbon composite material and preparation method thereof
CN113889595A (en) Preparation method of solid electrolyte coated graphite composite material
CN116621153A (en) Sodium ion battery biomass hard carbon anode material and preparation method and application thereof
CN114655951B (en) Preparation method of lithium ion battery cathode material
CN114122392B (en) High-capacity quick-charging graphite composite material and preparation method thereof
CN115275166A (en) Long-life graphite composite material and preparation method thereof
CN115663157A (en) Hard carbon composite material for lithium ion battery and preparation method thereof
CN114864897A (en) Quick-charging graphite composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination